The program is concerned with development of reactions and procedures in the carbohydrate field useful for synthesis of structures present in biologically important carbohydrate derivatives, and in understanding their biological role. A general objective is the establishment of reactions of high specificity that can be used, under mild conditions, for the structural conversion of common sugars and their derivatives into analogs of unusual functionality or stereochemistry that are present in numerous classes of natural carbohydrate derivatives, having importance in essential biological function and metabolism, or in therapeutic control. The reactions and procedures will facilitate partial and total syntheses of unusual sugars such as are present in various antibiotics, components of bacterial cell walls, antitumor agents, physiologically active glycosides, and sugar derivatives involved in metabolism; analogs of neurotransmission agents will be obtained optically pure by carbohydrate-based syntheses. Particular reactions for study include: specific oxidative procedures for introducing carbonyl functionality at selected sites in carbohydrates, deoxygenation methods, synthetic procedures employing unsaturated functionality, cycloaddition reactions, syntheses of chiral dioxolane and atrolactic aldehyde derivatives, reactions involving amination of sugars and transformations thereof, and transformations involving the dithioacetal group in sugar systems. Applications will include the total synthesis of various natural sugars, and the specific structural modification of physiologically active, complex carbohydrates, such as antibiotics, as a lead to novel structures of modified biological response, together with utilization of specialized spectral techniques for structure elucidation.